THERMOPLASTIC RUBBERS FOR THE MODIFICATION OF

BITUMENS: IMPROVED ELASTIC RECOVERY FOR HIGH

DEFORMATION RESISTANCE OF ASPHALT MIXES

C.P. Valkering,
Head, Bitumen Product Formulation and Application,
Koninklijke/Shell-Laboratorium, Amsterdam,
Shell Research B.V., The Netherlands

and
w. Vonk,
Leader, Bitumen/Polymer Group, Oil Products Department,
Koninklijke/Shell-Laboratorium, Amsterdam,
Shell Research B.V., The Netherlands

SUMMARY
Modification of bitumens with thermoplastic rubbers of the styrene-butadiene-styrene (SBS)
type increases the deformation resistance of asphalt mixes markedly, even if the modification
level is relatively low, e.g. 3 per cent. This phenomenon is closely related to the highly
elastic nature of SBS-modified binders. The effect of these binders in asphalt mixes was
studied in experiments in a Laboratory Test Track (LIT), which offers the closest simulation
of asphalt performance in practice. Unlike static creep testing, dynamic creep proved to give
a good correlation with the results obtained in the LIT. With the dynamic creep test, the
mechanism of deformation upon loading could be studied in detail. It was shown that the
elastic recovery upon deformation in the asphalt mix was significantly higher with the SBS-
modified binders than with the neat bitumens. Elastic recovery of the binders can be
demonstrated in a simple test using the ductilometer and thus the high efficiency of the SBS
was confirmed. Moreover, after the Rolling Thin Film Oven Test (RTFOT) the highly elastic
nature of these binders was maintained. Further, in comparison with their unmodified
counterparts, the SBS-modified binders showed improved performance after RTFOT in
terms of hardening. Ethylene/vinyl acetate (EVA) modified binders were also tested for
elastic recovery before and after RTFOT and were found not only to be less effective than the
SBS-modified binders but also to lose ductility and elastic recovery performance much more
rapidly.

PROCEEDINGS 15th ARRB CONFERENCE, PART 2

 Cees Valkering graduated in Experimental Physics from the
University of Amsterdam in 1966 and thereupon joined
Koninklijke/Shell-Laboratorium, Amsterdam, starting in the Bitumen
Department. Until 1974 he was engaged in the structural design and
evaluation of flexible pavements. Subsequently, he became involved
in Equipment Engineering and was sent on an assignment to Shell
International Marine in London. Returning to Amsterdam he joined
the Materials Research Department as a Group Leader in non-metallic
materials. In 1986 he rejoined bitumen research and is now head of
the section 'Bitumen Product Formulation and Applications'.
Willem Vonk joined Shell Research in 1968. He has a Polytechnic
degree in Chemical Engineering. He has been involved in many
aspects of bitumen and asphalt mix research and is currently leader
of the bitumen/polymer group in the Oil Products department at
Koninklijke/Shell-Laboratorium, Amsterdam. Vonk has (co)-
authored papers on the bitumen adhesion/detachment mechanism, on
the production and breaking mechanism of straight and polymer-
modified bituminous emulsions and on bitumen/polymer systems,
both for industrial and road applications.

2 PROCEEDINGS 15th ARRB CONFERENCE , PART 2

 INTRODUCTION

1. During the last thirty years, as a result of increas ing axle

loadings and traffic densities, rutting has in many countries become a
major cause of loss of serviceability of asphalt pavements . The correc-
tive measures taken to increase the rutting resistance of the pavements
have in general been the use of leaner mixes, sometimes in combination
with harder binders: in The Netherlands, for example, the specification
for the binde r content in dense wearing courses dropped from 7.25 to 6.00
parts by weight per hundred parts of aggregate over the period from 1962
to 1978. With the use of leaner mixes or harder binders , fatigue cracking
and fretting have become more important failure modes. It seems that the
minimum in terms of specified binder content has been reached or perhaps
even passed.

2. The deformation problem today has become even more severe and other
solutions are now being implemented. New developments in mix design and
the use of modified binders are currently not only envisaged, but also
increasingly being introduced. It is recognized and appreciated that the
performance limits of conventional bitumens have been reached for a
certain category of roads and that the use of polymers in bituminous road
binders provides a cost-effective solution (Downes et al. 1988).

3. The main object of adding polymers to binders for asphalt mixes is

to improve resistance to deformation by increasing the binder and mix
stiffness and/or by enhancing their elastic behaviour. If higher binder
contents in the mix are used, improvements in both the rutting resis-
tance and the fatigue and fretting resistances of the mixes may be
obtained.

4. Polymers which develop continuous networks in the bitumen are the

most effective in imparting elastic properties to the blend. In this
paper we report results obtained with CARIFLEX* TR-llOl, a block co-
polymer of the styrene-butadiene-styrene (SBS) type. Polymers which do
not form a network may also introduce an increased elasticity into the
binder, but only by a mechanism of stretching and recoiling of the mole-
cules; this mechanism will be less effective in media with low viscosi-
ties, i.e. at higher temperatures. For the ethylene/vinyl acetate (EVA)
type of polymer, for example, this explains the more elastic behaviour
at lower service temperatures, at which of course permanent deformation
is less important (Oliver and Witt) .

5. It is reported in this paper how the deformation resistance of the

asphalt mix is greatly improved by adding the SBS polymer to the binder,
even at low concentrations, and that this is attributed to the combined
effect of increased viscosity and elastic behaviour of the binder .
Properties of the fresh modified binders are reported together with
results obtained after high-temperature treatment in the Rolling Thin
Film Oven Test (RTFOT). Specific attention is given to the elastic
recovery of the modified binders as a measure of their elastic behaviour.

6. EVA-modified binders were included in a number of tests for

comparison .

* CARl FLEX is a Shell Trade Mark

PROCEEDINGS 15th ARRB CONFERENCE, PART 2 3

 THE EFFECT OF SBS ON BINDER PROPERTIES

GENERAL CONCEPT

7. For polymers which have no chemical interaction with the base

bitumen, a different interaction is necessary, which may be realised by
dissolving; however, this requires that t he solubility parameters of th e
polymer and of the base should be rather similar , which restricts the
type of suitable polymers considerably. Styrene and butadiene are com-
patible with the aromatic and non-aromatic components of the bitumen
respectively and it is this feature that produces the strong interac-
tions of SBS with bitumens.

8. SBS is unique in the sense that the different blocks ( Fig . 1) are
mutually incompatible and strive for phase separation. As they are
chemically bonded the blocks develop a phase s e parat ion on a micro-scal e
only; this phase separation leads to the joining of the poly styrene
end blocks of several molecules in domains. The polystyrene domains form
the physical crosslinking points of a three-dimens ional network of
polybutadiene (Fig. 2), which imparts to the polymer the properties
which are characteristic of vulcanised rubbers .

9. After blending with bitumen, the SBS swells - due to its strong
interaction with the bitumen constituents - b y up to nine times in
volume. This degree of swelling - which has been observed b y sep arating
the polymer-rich phase from the asphaltene-rich phase b y centrifuging at
elevated temperatures ( Vonk and Bull 1989) - is the highest at the lower
SBS concentrations. In this state and at pavement service temperatures ,
the SBS still maintains its characteristic elastic properties. At
concentrations of 5-6 %( w/ w) of SBS polymer , the swollen SBS takes a
major volume fraction in the binder and may form a continuous network
throughout the bitumen . At lower thermoplastic rubber (TR) contents, the
network may not be continuous throughout the bitum~n, but in fragmen ted
form it will still cover a significant volume fraction.

PO LYSTYREN E f\fVV\ POLYBUTAD IENE

Fig. 1 - Linear and branched thermoplastic rubber

4 PROCEEDINGS 15th ARRB CONFERENCE, PART 2

 Fig. 2 - Three-dimensional SBS network

10. The compatibility between the SBS and the base bitumen is not
related to the ability of the base to cause swelling of the polymer;
rather, it indicates the fact that the matrix left is stable during
high-temperature storage i . e . without precipitation of a phase rich in
asphaltenes . Additionally, blends of compatible bitumens with polymers
have proved to be somewhat more . ageing resistant (Blanken and Van
Gooswilligen 1980) .

PROPERTIES OF MODIFIED BINDERS

Materials

11. In this study bituminous binders have been modified by various

concentrations of the linear SBS polymer of medium molecular weight with
the Shell trade name CARIFLEX TR-l101 . For comparison, the same bitumens
have in a number of cases also been modified by an EVA compound which is
commercially available as a bitumen modifier .

12. Two bitumen types were used:

bitumen A as a base which is compatible with SBS i . e. during storage at
elevated temperature there is no segregation of a separate asphaltene-
rich phase;
bitumen B which is of Venezuelan origin, and which is not rated to
give storage-stable blends .
Different penetration grades of both bitumen types were tested.

PROCEEDINGS 15th ARRB CONFERENCE, PART 2 5

13. The polymers were blended into the base bitumens a t 18 5 °c using a
high-shear Silverson L2R disintegrator .

Properties

14. The properties reported and discussed in this paragraph are ma inly
the results of standard tests as used for the characterisation of road
binders . With such simple tests as Penetration ( pen ; fr e quent l y pen25 '
i . e. determined at 25 °C) and Softening Point (Ring & Ball : TR&B) ,
standard bitumens, defined as S-type b y Heukelom (Heukelom 19 69), a re
finger-printed rheologically and relevant properties such as v iscositi es
and stiffness moduli can be predicted satisfactorily by means of, for
example, the Van der Poe 1 Nomograph (Van der Poel 1954) . Polymers added
to a bitumen can often have - as intended - a marked effect on the
rheology and this makes the significance of the results of some of the
standard tests different from that for standard bitumens . This aspect
will receive attention in the discussions .

Viscosity and shear modulus

15. Like most polymers, SBS increases the viscosity of the bitumen b y
an interaction, which is mainly related to the size of the molecules and
their molecular design . The effect of different concentrations of the
polymer on different bitumen grades is shown in Fig. 3. At lower temper-
atures, where the SBS molecules are associated through the styrene
domains, the effect on rheology is still significant, becomes dependent
on loading conditions and may be appropriately described b y the stiffness

VISCOSITY , mPa.s

1000 T = 150 °c

100

BASE BITUMEN (TYPE A)

t:, 60 pen
o 100 pen
o 200 pen

o 2 4 6 8
'CARIFLEX ' TR - ll0l CONTENT, %

Fig. 3 - Effect of CARIFLEX TR-II0l content on blend viscosity

6 PROCEEDINGS 15th ARRB CONFERENCE, PART 2

 6SHEAR MODULUS, N/ m2
10

4
' 10

1000 ._._.--.--.~••• :;..:,.. % TR-ll0l

t=~:::.----:-:: ........;,: -
..........,,--
100 _
................ , - , '
............
-----
•... ,•.. ,. ... ,
0
3
5
10 7

0 .1 1 10
FR EQUENCY, Hz

Fig . 4 - Effect of CARIFLEX TR-llOl content on the shear modulus

of blends with 100 pen bitumen (Type A) at 40 °c
(Carri-Med rheometer)

modulus . Figure 4 give s the shear modulus as measured in the Carri-Med

r heometer at various fr equenci es and it is s hown that, und er these
conditions, an elastic plateau deve lops, even in a bl end containing not
more than 3 %(w/w) of SBS ; this plateau, where the modulus is more or
less independent of the loading time and frequency, corresponds to a
relatively smal l phase angle shift between applied stress and strain in
the measurement. These findings illustrate the effectiveness of the
modifier in giving elastic properties to the blend , e ven at low
concentrations whe r e b y a full continuous network is not formed .

Softening Point and Penetration

16. The Softening Point results in Fig. 5 , as obtained with different

SBS concentrations in three bitumen grades, revea l a marked increase in
the softening-point temperature at concentrations around 5 %; this i s
indicative of the formation of a full continuQus network throughout the
bitumen. For bitumens from other crude sources similar increases are
observed, but the concentra tion at which this happens varies
(Van Gooswi lli gen and Vonk 1 986). The Penetration decreases with
i ncreasing SBS concentration; this decrease is fairly linear in the
log (pen) versus concentrati on plot given in Fig. 6 and the formation of a
continuo us network does not show up in the penetration measurement. The
exp lanat ion fo r this is considered to be a non-linea r stress-strain
relatio n ship with SBS-modified binders : the continuous n e twork is
effective at the low stress levels in the Softe ning Point me asurement and
is not in the conditions of the Penetration test .

17 . In add i tion to the fact that the rheological tests which are
standard for conventional road bitumens do not give a vali d description
of modified binders , this non-linearity makes t he subj ect more complex,
as it is not yet certain which stress or strain levels are representa-
tive of the b inder conditions in aspha l t mixes .

PROCEEDINGS 15th ARRB CONFERENCE, PART 2 7

co

BASE BITUMEN (TYPE A) BASE BITUMEN (TYPE A)

(), 60 pen (), 60 pen
o 100 pen o 100 pen
o 200 pen o 200 pen

TR & S ' °c PENETRATION AT 25°C, 0.1 mm

100

80

100

-c 60
JJ
o
()
m
m
o 40
Z
G)
C/)
.....
~
:::J"
»
JJ
JJ
OJ 2 4 6 8 o 2 4 6 8
o 'CARIFLEX' TR - 1101 CONTENT, % 'C ARIFLEX ' TR - 1101 CONTENT, %
oz
.,.,
m
JJ
m
Z
o Fig. 5 - Effect of CARl FLEX TR-llOl content Fig. 6 - Effect of increasing contents
m
on softening point of CARlFLEX TR-llOl on the penetration
-C
» in different bitumen grades of bitumens of different grades
JJ
--1
N
Low temperature characterisation

18. The Fraass breaking point is affected favourably by the addition of

SBS, particularly with the softer bitumen (Fig. 7) . SBS increases the
cohesive stre ngth of the binder, which contributes to the results ob-
tained in the Fraass test, but additionally the very flexible polymer
polybutadiene - with a glass transition temperature around -90 °c -
reduces the brittleness of the blend at low temperatures. This is illu-
strated by the fact that, with SBS concentrations of 12 % or more, as
used in roofing applications, the Fraass temperature is generally below
-38 °C, even with base bitume ns as hard as 50 pen (-38 °c is the lower
limit of the test).

FRAASS BREAKING POINT, °C

o

-12

BA SE BITUMEN
-24 0 60 pen
11 100 pen
o 200 pen

-30L-------~------~-------L-------J
o 246 8
'CARIFLEX' TR-1101 CONTENT, %

Fig . 7 - Effect of CARIFLEX TR-llOl content on Fraass breaking point.

Bitumen Type A

Ductility

19. The ductility test on blends with SBS requires special attention.
This test is partly related to the bitumen's ability to flow: however ,
the SBS network may reduce this ability and, under certain conditions,
the ductility as defined by this test is less with SBS-modified bitumen
than with the unmodified base bitumen. The results in Fig . 8 reveal that
this situation is encountered at the higher temperatures, where the
extensions of the base bitumen cannot be followed by the SBS network. At
lower temperatures, however, where the base bitumen cannot sustain these
large extensions, the polymer enhances the flexibility and the ductility
increases with the addition of the polymer.

PROCEEDINGS 15th ARRB CONFERENCE, PART 2 9

 BASE' BITUMEN (TYPE A)
f'> 60 pen
o 100 pen
o 200 pen

- - - BITUMEN
- - BITUMEN + 5 % TR- 11 01

DUCTILITY, mm
f f
o ~
1400

1200

1000

800

600
,
I
I
I

,!
400
I

200 I
I
&_,l
o I
o 5 10 15
TEMPERATURE, °c

Fig , 8 - Effect of test temperature on the ductility of base bitumens

and bitumens modified with 5 % CARIFLEX TR-llOl

RUTTING RESISTANCE OF ASPHALT MIXES

20. Improvement of the rutting resistance of asphalt layers at the

higher service temperatures (25-50 °C) is at present the main objective
of polymer modification of the binder; as reported above, the addition
of the SBS polymer leads to a decrease in penetration , to an increase in
Softening Point temperature, to higher viscosities and to the develop-
ment of elastic behaviour in measurements of the shear modulus at low
loading frequencies. In this section we will briefly report on tests on
asphalt mixes which were made to quantify the e ffect of the binder
modification on the rutting resistance.

10 PROCEEDINGS 15th ARRB CONFERENCE , PART 2

21 . Our main tests for the assessment of the rutting stability of
asphalt mixes are performed in the Laboratory Test Track (LTT) at
Koninklijke/Shel l -Laboratorium, Amsterdam; in this circular unit moving-
wheel loadings are applied on pavements with a width of 0.7 m. At con-
trolled temperatures up to 60 °C, the rut formation can be followed as a
function of the number of wheel passes. Structures consisting of asphalt
layers 0 .07 m thick with cement-stabilised base layers have been tested
at 40 and 50 °C. The asphaltic mixes were kept the same in composition
(dense asphaltic concrete) but the binders were varied.

22. Results for the rutting resistance of the mixes containing polymer-
modifie d binders are shown in Fig . 9 in terms of the number of wheel
p a sses nece s sary for a rut depth of 10 mm to be reached in the tests at
40 and 50 °C. The data in F ig. 9 were obtained with type A base bitumens
and are a selection f ro m a series which has been publish ed by
Va n der Poe l (19 54). The plot s hows that the p avement life in terms of
r u tting increase s by a n order o f magnitud e on add ition of the p olymer to
the base bin der. Even if a s o fter base b itumen is se l ected to c omply with
t he re qu irements at l ower s ervice temper a ture s f o r certain climatic
c ondi t ions, a si gnificant improvement i n r u tting resistance is obtain ed.

BINDER PEN OF BASE (+ T R-ll0l J %)

0 1 0 mm RUT DE PT H REAC HE D
60 ( - ) L/LL TEMP. 40 DC

100 (-) // / //L/~

100 (3)

100 (5) / //

100 (7) //////////////////// / ////

200 (7) ////////////// / / ///////~

I I I I IIII I I I I I I I III I I I I I I I II
2 2 2
NUMBER OF WHEE L PASSES

F i g . 9 - Number of LTT whee l passes to a rut dep t h of 10 mm

for mi xes wi th different binders based on Type A bitumen

23 . As mentioned earlier, t h e meaning or validity of tests which are

standard for conventional bitumens has to be verified when these tests
are applied to modified binders . This same problem arises with tests on
asphalt mixes: for example, static creep tests on asphalt cylinders with
a compressive, uniaxial loading. For asphalt mixes with conventional
b i nders this test gives a proper rating of the stability of the mixes;
however, the strains obtained in this creep test at 40 °c versus the
time of loading (Fig . 10) for asphalt samples of the same composition
(dense asphaltic concrete), but with different levels of SBS in the
binder suggest that the SBS modification leads to a reduction in mix
stability.

PROC EEDINGS 15th ARRB CON FERENCE, PART 2 11

 3 TOTAL STRAIN, m/m
(5% 'C ARIFLE X' TR-1101)
(3% 'cARIFLEX' TR-1101)

(7% 'CARIFLEX' TR-1101)

(O% 'CAR IFLEX' TR-1101)

8L---L-----------~--------~~--------~
10 -10 2 103 104
LOADING TIME, s

Fig_ 10 - Strain in static creep tests at 40 °c on mixes

with different levels of CARl FLEX TR-1101 in the binder
(Type A. 100 pen)

24_ Since this is not in line with reality . a dynamic version of the
test with interrupted or transient loadings has been developed. This
test , which is reported in more detail in (Valkering et al. 1990),
includes a compressive , uniaxial loading pattern , as shown in Fig. 11 .

I---I d
.... ---
I I
STRESS I
I
I
I I I
I I /...100 kPa I I
I I I I
I I I I
Constant I I
l~ d l I ' ''fl''1
Preload
1 kPa
Itcyc l~ - 1. 2 or 4- s
I
I ~LOading
I
Time = 0.2 s
; I I t.. ~ ~

Total Strain
STRAIN
_,-,----~-~~~"l~Y~t~::::=-----~~I--'/·
, Residual St ra in .
I v
T ime

Fig . 11 - The dynamic creep test - schematic description

of loading and deformation

12 PROCEEDINGS 15th ARRB CONFERENCE , PART 2

Between loadings there is sufficient time for the recovery of the spec i -
men, thus avoiding interaction between the recovery and the subsequent
loading. The test, with loading time of 0.2 s, a loading cycle tcrcle of
2 s and a loading stress of 0.1 MN/m2, indeed gives lower residua
strains at the end of the test on samples with SBS-modified binders; the
test duration has been set at one hour and thus includes 1800 load
repetitions. It is noted that the end faces of the samples are polished
and treated to minimise friction with the loading plates and thus ensure
a uniaxial stress condition.

25. The residual strain in the dynamic creep test correlates with the
rutting under a moving wheel as measured in the LTT. This correlation is
evident from Fig. 12, which shows the residual strain in the creep test
versus the rut depth at the end of tests in the LTT for experiments at
40 and 50 °C .

-1
RESIDUAL STRAIN
10.-
I- OPEN SYMBOLS = 40°C
Sf- SOLID SYMBOLS = 50 °c
f-
6f-
l- • ,~

4f- 0
... • 0
f- • <l
t>
0 CONVENTIONA L
80 / 100
& 0 60 pen
2f- ~ iOO pen

...•
(; <> iOO pen + 3 % TR
100 pen + 5 % TR
(; iOO pen + 7 % TR

-2
10 1 I I I I I I I
• 200 pen + 7 %
I
TR

2 3 4 5 6 7 S 910 2
RUT DEPTH, mm

Fig . 12 - Correlation between residual strain in dynamic creep test

and rut depth in LTT tests . Bitumen Type A

26. The increased recovery with SBS-modified binders is considered to

be the explanation for the improved resistance to permanent deformation
of mixes with such binders . This is supported by Fig. 13, which shows
the recovery of the asphalt sample after one of the loadings in the
final stage of the dynamic creep test expressed as a percentage of the
total strain caused by that loading. Although the percentage recovery
exceeds 99 % even on mixes with non-modified binders, the residual, i.e .
complementary, part of the deformation is significantly smaller with the
modified binders. This conclusion explains the emphasis on the recovery
in the next paragraph.

PROCEEDINGS 15th ARRB CONFERENCE, PART 2 13

 BINDER (TYPE AND PEN OF BASEI % SBS)

A,209/ 7

A, 9717

A, 97/5

A, 97/ 3

-
A, 48/ 0

A, 97/ 0
I

90.00 90. 50 100.00

RECOVERY, %

Fig, 13 Percentage recovery of deformation measured

during the final stages of the dynamic creep test

ELASTIC RECOVERY OF THE BINDER

27, The recovery of the deformation after release of the loading is a

measure of the elastic behaviour of the binder and is related to the
elastic plateau as observed with the Carri-Med (Fig , 4) and to the phase
angle between stress and strain. Various test methods may be employed to
demonstrate elastic recovery (Downes et al. 1989; Vonk and Van
Gooswilligen 1989), but in this paper we will focus on the one which is
gaining ground in Europe: the ductility recovery test, in which existing ,
readily available bitumen testing equipment is used (Ref. 10), The method
employed is fairly simple: a ductility test specimen is elongated up to a
certain specified length and cut into two halves; after one hour of
recovery, the elastic recovery is measured as a percentage of the applied
strain, Generally, this test is carried out at fairly low temperatures;
thus the compliance with a minimum ductility specification is established
at the same time.

FRESH PROPERTIES

28, The results obtained with blends with different types of bitumens
and with various concentrations of the modifier are reported in Table I.
The recoveries reported were determined - in separate tests - with
initial elongations of 0 . 2 and 0,5 m,

29 . The data reveal that a significant increase in recovery is realised

even at modifier concentrations as low as 3 %. The increases obtained
with EVA are less pronounced than with SBS, particularly in the less
compatible bitumen. The recovery of the SBS-modified bitumens appears
not to depend very much on bitumen type and grade .

14 PROCEEDINGS 15th ARRB CONFERENCE, PART 2

 TABLE I

PROPERTIES OF BINDERS BEFORE AND AFTER RTFOT

Property Bitumen A Bitumen B

- SBS EVA - SBS EVA

3% 7% 3% 7% 3% 7% 3% 7%

Before RTFOT

pen25' 0.1 mm 99 86 67 107 123 79.5 61 41,.5 77 83

TR&B' °c 42 48 90 43 48.5 47 53.5 87 46 . 5 56

Ductility recovery
at 13 °c after
e longation of:
20 cm, % 5 74 96 49 74 17 78 90 48 52
50 cm, % 4 82 97 52 63 8 79 91 43 (1)

After RTFOT

p en 25 ' 0. 1 mm 67 58 52 78 87 48 42 33.5 42.5 48

TR&B' °c 44.5 48 87 46 49.5 50.5 58 82.5 56 66

Loss on h eat, %m -0 .08 -0.08 -0 .06 0 .07 0.21 0 . 24

Retained p e n, % 68 67 78 73 71 60 69 75 55 58
e:. TR&B' °c 2.5 0 -3 3 1 3. 5 4.5 -4.5 9.5 10

Ductility recovery
at 13 °c after
elongat ion of:
20 c m, % 75 90 46 70 72 76 44 (2)
50 cm, % 82 93 48 61 72 (3) (4) (2)

(1) ductility failure after 26 cm e l ongation (48 % recovery).

(2) ductility fa ilu re after 1 2 c m elongation (36 % r~covery).

(3) ductility failure after 33 c m elongation (74 % recovery).

(4) ductility failure after 28 c m elongation (36 % recove~y).

30. It is surprising that the EVA modification seems to result in a

reduction of the hardness as measured in the penetr atio n test .

PROCEEDINGS 15th ARRB CONFERENCE, PART 2 15

PROPERTIES AFTER RTFOT

31. The properties of the binder in the mix are more relevant than
those of the fresh binder. Therefore we report also the properties
obtained after the Rolling Thin Film Oven Test, which may be considered
as a simulation of hot mix operation. It is generally accepted that the
results obtained in this test on SBS-modified bitumens compare favourably
with those on unmodified ones, the assumption being that the hardening
effect of the bitumen is partly undone by some loss of SBS effectiveness,
which is, however, not quantified. The recovery of the modified binders
has now been measured after the RTFOT to verify the degree of the loss in
effectiveness of the binder modification.

32. The results are reported in the Table I and in Figs. 14 and 15, in
which the recoveries before and after RTFOT have been plotted versus the
SBS content for the two 80/ 100 pen grade bitumens.

33. The data reveal that:

- the changes in properties as a result of the RTFOT are affected
by bitumen quality . The use of the compatible, special bitumen gives
better results than the type B (Venezuelan) bitumen, which is a
confirmation of earlier findings (Blanken and Van Gooswilligen 1980) ;

DUCTILITY RECOVERY, %
iOO BEFORE RTFOT

",,_- --~
AFTER RTFOT
:;.0'"
80 o

60

40

20

2 4 6
TR- 1101 CONTENT, %

Fig. 14 - Ductility recovery after 200 mm elongation at 13 °C,

before and after RTFOT .
Bitumen Type A

16 PROCEEDINGS 15th ARRB CONFERENCE, PART 2

 DUCTILITY RECOVERY, %
100
BEFORE RTFOT

80

60

40

20

t 2 4 6
TR-ll0l CONTENT, %

Fig . 15 - Ductility recovery after 200 mm elongation at 13 °C,

before and after RTFOT.
Bitumen Type B

the SBS-modified bitumens generally behave better than their unmodified

counterparts with respect to hardening in terms of Softening Point
increase and penetration drop;
in the special bitumens the effect of EVA was also favourable in this
regard; in the B-type bitumens, though, the effect of EVA was slightly
unfavourable;
- the elastic recovery of the SBS-modified binders was still high after
RTFOT (>70 %), whereas that of the EVA-modified binders, particularly
with the B-type bitumens, dropped dramatically;
the ductility of the EVA-modified binders in the B bitumens was
considerably reduced after RTFOT and down to levels below those given
in European specifications; at the same time, their elastic recovery
after breaking was between 35 and 45 % only .

34. On the basis of these results it may be deduced that in the

mechanisms that contribute to an increased resistance to permanent
d efo rmation of asphalt mixes - increased stiffness and elasticity - the
effect of EVA is less pronounced in the elasticity and should basically
be sought in an increased stiffness of the mix.

PROCEEDINGS 15th ARRB CONFERENCE, PART 2 17

 CONCLUSIONS

35 . It has been shown that the modification of road binders with the
linear SBS copolymer CARIFLEX TR-llOl leads to significant changes in the
rheological properties of the binder, even at concentrations as low as
3 %. The effectiveness of the bitumen modifier is ascribed to the
development of a polymer-rich phase that may be regarded as a strongly
extended polymer .

36. Results of standard tests for the rheological characterisation of

road binders do not necessarily have the same meaning when used on
modified binders . One complication is that the SBS-modified binders seem
to have a non-linear stress-strain relationship .

37 . From rutting experiments and from creep tests it was earlier con-
cluded that the significant increase in rutting resistance of mixe s with
modified binders could be ascribed to the increased recovery of the
deformation of the asphalt mix after release of the loading, which
explains the emphasis on recovery measurements in this paper . Tests on
samples in the ductilometer (which measures elastic recovery after
elongation) confirmed the high efficiency of the SBS modification in
increasing the elastic recovery of the blends.

38. These tests on modified binder samples exposed to the conditions of

the RTFOT showed only a small reduction in this ability to recover, indi-
cating that, under the conditions of mix production and application, the
breakdown of SBS elastomer is relatively small.

39. The modified binders also perform better in relation to the speci-
fication on hardening in the RTFOT than the base bitumens .

40. The effect of the SBS on the properties of the final blend before
and after RTFOT is also influenced by the type of base bitumen : general-
ly, the properties of the blends based on a special, compatible base are
more favourable than those of blends with a non-compatible base .

41 . The comparative tests on EVA-modified binders revealed lower

ductility values, lower recovery values, and more hardening in the RTFOT
than for binders with SBS.

18 PROCEEDINGS 15th ARRB CONFERENCE, PART 2

 REFERENCES

1. DOWNES, M.J.W., KOOLE, R . C., MULDER, E.A. and GRAHAM, W.E . (1988) .
Some proven new binders and their cost effectiveness. Proceedings of
the VIIth AAPA International Asphalt Conference, Brisbane ,
7-11 August 1988, pp . 119-132.
2. OLIVER, J . W.H . and WITT, H.P . The interpretation of elastometer test
results. ARRB Internal Report AIR 286-13.
3 . VONK, W.C. and BULL, A. L . (1989). Phas e phenomena and concentration
effects in blends of bitumen and SBS elastomer. Proceedings of the
VIIth International Roofing Congress, Munchen, 30 May - 1 June 1 989,
pp. 210-222.
4. BLANKEN, T.C . and VAN GOOSWILLIGEN, G. (1980). Bitumen/ polymer blends
for premium-quality roofing products and s y stems . Proceedings of
the 1st International Congress on Waterproofing, Barcelona,
12 - 14 May 1980, pp. 196-223.
5. HEUKELOM , W. (1969). A bitumen test data chart for showing the effect
of temperature on the mechanical behav iour of asphaltic bitumens . J.
Inst. Petr . , 55 (546) pp . 404-417.
6. VAN DER POEL, C. (1954) . A general system describing the visco-
elastic properties of bitumen and its relation to routine test data ,
J. Appl. Chern . , 4, pp . 221-236.
7 . VAN GOOSWILLIGEN , G. and VONK, W. C. (1986). The role of bitumen in
blends with thermoplastic rubbers for roofing applications. Paper
presented at the VIth International Conference 'Roofing and
Waterproofing Worldwide', London, 30 April - 2 May 1986 ; SIPC Supply
and Marketing Publication No . 86/13, SIPC, London .
8. VALKERING, C. P., LANCON, D.J.L ., DE HILSTER, E. and STOKER , D.A.
(1990). Rutting resistance of asphalt mixes containing
non-conventional and polymer-modified binders . Paper presente d
at the AAPT meeting, Albuquerque, 19 - 21 February 1990 .
9 . VONK, W.C . and VAN GOOSWILLIGEN, G. (1989) Improvement of paving
grade bitumens with SBS polymers . Proceedings of the IVth Eurobitume
Conference, Madrid, 4 - 6 October 1989 , pp . 298- 303 .
10 . Technische Lieferbedienung PmB von Asphaltschicht im Heiss einbau .
Teil 1, Gebrauchsfertige PmB . TL PmB part 1.

PROCEEDINGS 15th ARRB CONFERENCE, PART 2 19